Detergent compositions containing particle deposition enhancing agents

ABSTRACT

DETERGENT COMPOSITIONS CONTAINING WATER-INSOLUBLE PARTICULATE SUBSTANCES, SUCH AS ANTIMICROBIAL AGENTS, AND CERTAIN CATIONIC POLYMERS WHICH SERVE TO ENHANCE THE DEPOSITION AND RETENTION OF SUCH PARTICULATE SUBSTANCES ON SURFACES WASHED WITH THE DETERGENT COMPOSITION.

United States Patent 3,580,853 DETERGENT COMPOSITIONS CONTAININGPARTICLE DEPOSITION ENHANCING AGENTS John J. Parran, Jr., SpringfieldTownship, Hamilton County, Ohio, assignor to The Procter & GambleCompany, Cincinnati, Ohio No Drawing. Filed Sept. 27, 1967, Ser. No.671,117 Int. Cl. C11d 3/22, 3/48 US. Cl. 252-152 Claims ABSTRACT OF THEDISCLOSURE Detergent compositions containing water-insoluble particulatesubstances, such as antimicrobial agents, and certain cationic polymerswhich serve to enhance the deposition and retention of such particulatesubstances on surfaces washed with the detergent composition.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is related tothe earlier-filed copending application of John J. Parran, Jr., Ser. No.476,175, filed July 30, 1965, now abandoned.

BACKGROUND OF THE INVENTION The field of this invention is detergentcompositions including shampoos (liquid and cream), laundering,hardsurface and dishwashing detergents (granular and liquid), andpersonal use toilet detergent bars.

Various water-insoluble particulate substances have been incorporated indetergent products for the purpose of imparting some residual propertyor characteristic on surfaces washed with the products. For example,shampoo compositions containing particulate antidandruif agents havebeen developed which function by deposition and retention of theparticulate agent on the hair and scalp during shampooing. Sufficientquantities of the deposited particulate agents are retained afterrinsing to impart some degree of residual antimicrobial activity to thewashed hair and scalp. Such antidandruff shampoo compositions aredisclosed, for example, by Karsten, Taylor and Parran in US. Pat.3,236,733, granted Feb. 22, 1966.

Particulate antimicrobial substances have also been used in variouslaundry detergents and personal use toilet detergent bars to impartresidual antimicrobial activity on the fabrics or skin surfaces washedwith same. Such products are disclosed by Reller and Jordan in US. Pats.3,134,711, granted May 26, 1964, and 3,256,200, granted June 14, 1966.

Various other water-insoluble or sparingly soluble particulate materialssuch as sunscreens, fabric brighteners, and whiteners have been employedin detergent compositions and depend for their activity on particledeposition and retention on washed surfaces.

It is apparent that an effective detergent composition, properly used,will by its very nature tend to minimize retention of particulate matteron washed surfaces. Thus, only a relatively small proportion ofparticles present in such detergent compositions are actually retainedafter rinsing of the washed surface. Since the activity of antimicrobialand other particulate agents is in part a function of the quantity ofparticles deposited and retained on the involved surfaces, measureswhich enhance deposition and/or promote retention of such particlesserve to reduce the quantity of the substance in the compositionrequired to attain a given level of activity or increase the activityattainable with a given concentration of such particles.

SUMMARY OF THE INVENTION It has now been discovered that water-solublecationic nitrogen-containing polymers having a molecular weight withinthe range from about 2,000 to about 3,000,000, and having a cationiccharge density (as defined hereinafter) greater than .001 in aqueoussolution, enhance the deposition and retention of water-insoluble orsparingly soluble particulate substances contained in detergentcompositions on surfaces washed therewith.

Although the mechanism whereby this phenomenon occurs is not fullyunderstood, it is believed that the polymer coats or attaches itself insome way on the involved particles imparting a net positive chargethereto which increases the aflinity of the particle for the generallynegatively charged washed surfaces.

It is therefore an object of this invention to provide detergentcompositions which have improved capacities to impart residual activityor properties to surfaces washed therewith.

It is a further object of this invention to provide improved detergentcompositions containing water-insoluble or sparingly soluble particulatesubstances which are deposited and retained on washed surfaces.

It is yet another object of this invention to provide a method forenhancing the deposition of particulate substances from detergentcompositions and the retention of such substances on surfaces washedtherewith.

These and other objects will become apparent from the following detaileddescription of the invention.

DETAILED DESCRIPTION OF THE INVENTION The detergent compositions of thisinvention are comprised of (1) an organic surface active agent(surfactant, i.e., detergent compound); (2) at least one water-solublecationic nitrogencontaining polymer having a molecular weight within therange from about 2,000 to about 3,000,000 and having a cationic chargedensity greater than .001 in aqueous solution; and (3) a water-insolubleor sparingly soluble particulate substance capable of imparting adesired residual property to a surface to which it becomes afiixed.

In its process aspect, this invention is a method for enhancing thedeposition and retention of particulate substances upon surfaces washedwith a detergent composition containing same, comprising uniformlyadmixing said particulate substances with a water-soluble cationicnitrogen-containing polymer having a molecular weight within the rangefrom about 2,000 to about 3,000,000, and having a cationic chargedensity greater than .001'in aqueous solution, and incorporating saidmixture in a detergent base.

The cationic charge density of a polymer as that term is used hereinrefers to the ratio of the number of positive charges on a monomericunit of which the polymer is comprised to the molecular weight of saidmonomeric unit, i.e.,

cationic charge density number of positive charges monomeric unitmolecular weight of organic sulfuric reaction products having in theirmo- I lecular structure an alkyl group containing from about 8 to about20 carbon atoms and a sulfonic acid or sulfuric acid ester radical. Suchsurfactants include the sodium, potassium, and triethanolamine alkylsulfates, especially those derived by sulfation of higher alcoholsproduced by reduction of tallow or coconut oil glycerides; sodium orpotassium alkyl benzene sulfonates, especially those of the typesdescribed by Gunther et al. in US. Pat. 2,477,383, granted July 26,1949, in which the alkyl group contains from about 9 to about carbonatoms; sodium alkyl glyceryl ether sulfonates, especially those othersof higher alcohols obtained from tallow and coconut oil; sodium coconutoil fatty acid monoglyceride sulfates and sulfonates; sodium salts ofsulfuric acid esters of the reaction product of one mole of a higheralcohol (i.e., tallo'w or coconut oil alcohols) and about 3 moles ofethylene oxide; and the water-soluble salts of condensation products offatty acids with sarcosine, e.g., triethanolamine N-acyl sarcosinate,the acyl radicals being derived from coconut oil fatty acids.

Preferably, anionic organic surfactants of the high sudsing type areused for the shampoo embodiments of this invention. Thus, alkyl glycerylether sulfonates, N-acyl sarcosinates, and alkyl ether ethylene oxidesulfates as described above are used to special advantage. These and theforegoing surfactants can be used in the form of their sodium, potassiumor lower alkanolamine (e.g., mono-, di, and triethanolamine) salts.

Conventional soaps are also operable anionic surfactants for 'thepurposes of this invention. Suitable soaps include the water-solublesalts, e.g., sodium, potassium, and lower alkanolamine salts of fattyacids occurring'in coconut oil, soybean oil, castor oil or tallow, orsyntheti cally produced fatty acids may be used.

Polar nonionic surfactants can be used herein, either alone or inadmixture with anionic and/or ampholytic surfactants. Surfactants ofthis class can serve to enhance lathering and cleaning properties ofanionic detergents. By polar nonionic surfactant is meant asurfacsurfactant molecule bears no net charge and does not dissociateinto ions.

A preferred polar nonionic surfactant for use in the presentcompositions is amine amine oxide of the general formula R R R N O,wherein R is an alkyl, alkenyl, or monohydroxyalkyl radical having fromabout 10 to 16 carbon atoms, and R and R are each methyl, ethyl, propyl,ethanol or propanol radicals. An especially preferred amine oxide isdodecyldimethylamine oxide.

Other operable polar nonionic surfactants are the phosphine oxideshaving the general formula R R R P-' O, wherein R is an alkyl, alkenylor monohydroxyalkyl radical ranging in chain length from 10 to 18 carbonatoms, and R and R are each alkyl or monohydroxyalkyl radicalscontaining from 1 to 3 carbon atoms. A preferred phosphine oxide isdodecyldimethyl phosphine oxide.

Suitable amphoteric surfactants include the alkylbetaiminodipropionates, RN(C H COOM) alkyl beta-aminopropionates, RN(H)CH COOM; and long chain imidazole derivatives having the general formula:

In each of the above formulae, R is an acyclic hydrophobic groupcontaining from about 8 to about 18 carbon atoms and M is a cation toneutralize the charge of theanion, e.g., alkali metal such as sodium andpotassium and ammonium and substituted ammonium cations.

Specific operable amphoteric surfactants include the (11'. sodium saltof lauroyl-cycloimidinium-l-ethoxy-ethionic acid 2 ethionic acid,dodecyl beta-alanine, and the inner salt of Z-trimethylamino lauricacid. As zwitterionics, the substituted betaines such as alkyl dimethylammonio acetates wherein the alkyl radical contains from about 12 toabout 18 carbon atoms can also be used. Several examples of this classof zwitterionic surfactants are set forth in Canadian Pat. 696,355,granted Oct. 20, 1964.

Especially preferred shampoo compositions in accord ance with thisinvention will contain a non-soap anionic organic surfactant at aconcentration of from about 8% to about 30% by weight of the totalcomposition.

Although nonionic and cationic surfactants are not preferred for thepurposes of this invention they can nevertheless be used withoutsubstantial loss of the advantageous effects of the cationic polymers ondeposition and retention of particulate matter on washed surfaces.Nonionic surfactants may be described as compounds produced by thecondensation of alkylene oxide .groups (hydrophilic in nature) with anorganic hydrophobic compound, which may be aliphatic or alkyl aromaticor alkyl aromatic in nature. As those skilled in the are are well aware,the length of the hydrophilic or polyoxyalkylene radical required forcondensation with any particular hydrophobic group can be readilyadjusted to yield a water-soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic elements.

For example, a well known class of nonionics is made available on themarket under the tradename of Pluronic! These compounds are formed bycondensing ethylene oxide with a hydrophobic base formed by thecondensation of propylene oxide with propylene glycol. The hydrophobicportion of the molecule, of course, exhibits-water insolubility. Themolecular weight of this portion is-of the order of 950 to 4,000. Theaddition of polyoxyethylene radicals to this hydrophobic portion tendsto increase thewater solubility of the molecule as a whole. Liquidproducts are obtained up to the point where polyoxyethyl'ene content isabout 50% of the total weight of the condensation product.

Suitable nonionics also include the polyethylene oxide condensates ofalkyl phenols, e.g., the condensation prod-- nets of alkyl phenolshaving about 6 to 12 carbon atoms, either straight chain or 'branchchain, in the alkyl group with ethylene oxide in amounts equal to 10 to25 moles of ethylene oxide per mole of alkyl phenol. The alkylsubs-tituent in such compounds may be derived from polym* erizedpropylene, diisobutylene, octane, or nonane, for example.

Other suitable nonionics may be derived by the condensation of ethyleneoxide with the product resulting from the reaction of propylene oxideand ethylene diamine. Here again, a series of compounds may be produced,depending on the desired balance between hydrophobic and hydrophilicelements. For example, compounds (molecular weight from about 5,000 toabout 11,000) of about 40% to polyoxyethylene content and resulting fromthe reaction of ethylene oxide groups with a hydrophobic baseconstituted of the reaction product of ethylene diamine and excesspropylene oxide, said base having a molecular weight of the order of2,500 to 3,000, are satisfactory.

Further satisfactory nonionics include the condensation product ofaliphatic alcohols having from 8 to 18 carbon atoms, either straightchain or branch chain, with ethylene oxide, an example being a coconutalcohol/ ethylene oxide condensate having from 10 to 30 moles ofethylene oxide per mole of coconutalcohol, the coconut alcohol fractionhaving from 10 to 14 carbon atoms.

Cationic surfactants which can be used in the compositions of thisinvention include distearyl dimethyl ammonium chloride, stearyl dimethylbenzyl ammonium chloride, coconut alkyl dimethyl benzyl ammoniumchloride, dicoconut alkyl dimethyl ammonium chloride, cetyl pyridiniumchloride, and cetyl trimethyl ammonium bromide.

As hereinbefore indicated, the compositions of this invention contain asan essential component a water-soluble cationic nitrogen-containingpolymer having a molecular weight within the range from about 2,000 toabout 3,000,- 000 and a cationic charge density greater than .001 inaqueous solution.

Operable cationic polymers for the purpose of this invention includepolyethylenimine or alkoxylated polyethylenimine polymers. It isbelieved that the structural formula of the backbone of polyethylenimineis:

wherein x represents a whole number of sufiicient magnitude to yield apolymer of molecular weight greater than about 2,000. Branch chainsoccur along the polymeric backbone and the relative proportions ofprimary, secondary and tertiary amino groups present in the polymer willvary, depending on the manner of preparation. The distribution of aminogroups in a typical polyethylenimine is approximately as follows:

The polyethylenimine is characterized herein in terms of molecularweight. Such polymers can be prepared, for example, by polymerizingethylenimine in the presence of a catalyst such as carbon dioxide,sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid,acetic acid, etc. Specific methods are described in US. Pat. Nos.2,182,306, Ulrich et al., granted Dec. 5, 1939; 3,033,746, Mayle et al.,granted May 8, 1962; 2,208,095, Esslemann et al., granted July 16, 1940;2,806,839, Crowther, granted Sept. 17, 1957; and 2,553,696, Wilson,granted May 21, 1951. Polyethylenimine has a cationic charge density of.004 in aqueous solution at pH 7.0.

Similarly, alkoxylated polyethylenimine can be prepared, for example, byreacting one part by weight ethylene oxide or propylene oxide with onepart by weight of polyethylenimine prepared as described above andhaving a molecular weight greater than about 2,000. Preferably, theweight ratio of polyethylenimine to alkylene oxide is at least about1:1. If this ratio is less than about 124 the cationic charge density ofthe polymer in aqueous solution will not be greater than .001 as isrequired for the purpose of this invention. A preferred ethoxylatedpolyethylenimine has a molecular weight of about 80,000 to 120,000 and acationic charge density of .004 in aqueous solution at pH 7.0.

Yet another class of water-soluble cationic nitrogencontaining polymerswhich can be used in the practice of this invention are those in whichat least 30 mole percent of the molecular structure is composed ofmonomeric units containing one or more quaternary ammonium groups andany balance of which is comprised of non-quaternized polymeric unitsderived from monoethylenically unsatu rated monomeric groups. The degreeof quaternization must be suflicient to provide a cationic chargedensity greater than about .001. Such polymers include, for example,quaternized polyvinylimidazole, quaternized poly-(dimethylaminoethylmethacrylate), quaternizedpoly(diethylaminoethylmethacrylate), quaternized poly(pdimethylaminomethylstyrene) and others disclosed by Lang in US. Pat.3,313,734, granted Apr. 11, 1967, all having molecular weights withinthe range from about 2,000 to 3,000,000.

Still other types of water-soluble cationic polymers useful herein arethe following:

(1) Water-soluble quaternary nitrogen-substituted cel-*Hydroxyethyleellulose Hydroxyethylcellulose is, of course, comprised ofhydroxyethyl-substituted anhydroglu'cose units with varying degrees ofhydroxyethyl substitution. This material is pre pared by reactingalkaline cellulose with ethylene oxide as is more fully described byGloor et al., Ind. Eng. Chem., 42:2150 (1950). The extent ofsubstitution with the quaternary nitrogen-containing group must besufficient to provide a cationic charge density greater than .001, andthe molecular weight of the substituted hydroxyethylcellulose polymermust be within the range from about 2,000 to 3,000,000.

The preferred cellulose ether derivative from which the quaternaryammonium-substituted polymers described above are prepared include thosewhich are water-soluble nonionic lower alkyl or hydroxyalkylsubstituted. Such derivatives include methylcellulose, ethylcellulose,and hydroxyethylcellulose.

A particuarly efficacious quaternary ammonium-substituted celluloseether derivative for the purpose of this invention is available fromUnion Carbide under the code name JR-lL. This polymer has a molecularweight within the range from 100,000 to 1,000,000 and a cationic chargedensity of .005. Polymer JA-1L is a cationic cellulose ether having thestructure:

wherein R is a residue of an anhydroglucose unit, Wherein Y is aninteger from 50 to 20,000 and wherein each R individually represents asubstituent of the general formula:

wherein m is an integer from 0 to 10, n is an integer from 0 to 3, and pis an integer from 0 to 10. The average values per hydroglucose unitare: n is from 0.35 to 0.45

and the sum of m-l-p is from 1 to 2.

(2) Water-soluble linear polyamines available from The Rohm & HaasCompany under the trade name Primafloc C3. This polymer has a molecularweight within the range from about 30,000 to 80,000 and a cationiccharge density in aqueous solution at pH 7.0 greater than .001, andcontains at least 50 mole percent of units of the formula the NalcoChemical Company under the trade names Nalco 600 and Nalcolyte 605. Suchpolymers have the formula:

L AH J. wherein x is an integer of sufiicient magnitude to yield apolymer having a viscosity at 74 F. of 21 to 42 centipoise. Thesepolymers have a molecular Weight within the range from about 2,000 to3,000,000 and a cationic charge density greater than .001 in aqueoussolution at pH 7.0.

(4) Coagulant Aid #225 commercially from The Calgon Company. Thisproduct is a water-soluble nitrogencontaining polymer having a molecularweight within the range from about 30,000 to 3,000,000 and a cationiccharge density greater than .001 in aqueous solution at pH 7.0.Coagulent Aid #225 is a condensation polyethylene amine extended withepichlorohydrin and prepared as follows: A l-liter flask was fitted witha stirrer, reflux condenser, thermometer, and an addition funnel, and232 g. of Amine E-100 was introduced. This is a product of Dow ChemicalCompany containing about 10% tetraethylenepentamine, about 40%pentaethylenehexamine, about 20% cyclized polyalkylene, polyamines, andabout 10% polyalkylene polyamines having chains greater thanpentaethylene (mostly hexaethyleneheptamine and heptaethyleneoctamine)250 g. of water was added and the solution heated to reflux. To thesolution was added, at a suitable rate, 60 g., 0.6 mole, of ethylenedichloride. The addition rate of the EDC was carefully controlled sothat a minimum of unreacted EDC excess was maintained. On completion ofEDC addition the reaction mixture was held at 100-110 for one hour. Thereaction product at this point was a prepolymer as above described.

The prepolymer formed as above was heated to 80 C. and the dropwiseaddition of 37 g., 0.4 mole, of epichlorohydrin (ECH) was begun. Thetemperature was allowed to rise no higher than 90 during the addition.On completion of the addition the reaction mixture was held at 100 for30 minutes. The resulting polymer, was a 57.5% active solution 'with aviscosity of 2,000 cps.

(5) Conductive Polymer #261 commercially available from The CalgonCompany. This product is a water-soluble nitrogen-containing polymerhaving a molecular weight within the range from about 30,000 to3,000,000 and a cationic charge density greater than .001 in aqueoussolution at pH 7.0. Conductive Polymer #261 ispoly(N,N-dimethyl-3,5-methylene piperidinium chloride), averagemolecular weight 50,000.

If the molecular weight of the cationic polymers em.- ployed herein isless than about 2,000, no substantial enhancement of particle depositionoccurs. Best results are obtained with polymers having 'a'molecularweight within the range from about 30,000 to about 1,000,000.

The cationic polymer can be employed herein at a concentration withinthe range from about 0.1% to about 10.0% by weight, preferably" fromabout 0.25% to about 4.0% by weight.

Particulate substances which can be used in the detergent compositionsof this invention preferably have an average particle diameter withinthe range from about 0.2 to about 50 microns and include water-insolubleor sparingly soluble anti-microbial agents, sunscreens, fabricbrighteners, and various substances which create a favorable skin feelafter washing. These particulate substances depend on deposition andretention on washed surfaces to produce their intended elfect.

Particulate antimicrobial substances, the deposition and retention ofwhich is enhanced by the cationic polymers described herein include, forexample, (a) substituted salicylanilides having the general formula:

Y OH (I? Y Y X Y 8 wherein X is hydrogen or halogen, and Y is hydrogen,halogen or trifluoromethyl; (b) substituted carbanilides having thegeneral structural formula:

X Xu

wherein X is a halogen and n is an integer from 1 to 3, R is an alkyleneradical having from 1 to 4 carbon atoms or divalent sulfur; and (d)mixtures of (a), (b), and (c).

The salicylanilides encompassed by (a) above include3,4,S-tribromosalicylanilide; 5bromosalicyl-3,5-di(trifluoromethyDanilide; 5 chlorosalicyl3,5-di(trifluoromethyl)anilide; 3,5 dichlorosalicyl-3,4-dich1oroanilide;and 5-chlorosalicyl 3 tri-fluoromethyl-4-chloranilide. These and othersalicylanilides useful herein are disclosed by Bindler and Model in U.S.Pat. 2,703,332, granted Mar. 1, 1955.

The preferred carbanilides of (b) above include 3,4,4-trichlorocarbanilide; 3 trifluoromethyl-4,4-dichlorocarbanilide; 3trifluoromethyl-3,4,4'-trichlorocarbanilide; 3,3'-bis(trifluoromethyl) 4ethoxy 4' chlorocarbanilide; and 3,5 bis(trifluoromethyl) 4chlorocarbanilide.

The compounds in (c) above in which R represents an alkylene radical aremore fully described in U.S. Letters Patent 2,555,077, granted Dec. 26,1950. The preferred compounds of the general class of (0) above arethose which are symmetrical in structural configuration, such as bis(Schloro-Z-hydroxyphenyl) methane,bis(3,5-dichloro-2hydroxyphenyl)methane, bis(3,5,6 trichloro-Z-hydroxyphenyl)methane, bis(3,5 dichloro 2-hydroxyphenyl) sulfide, bis(3,5,6-trichloro-2-hydroxyphenyl)sul fide, and mixtures thereof.

Additional antimicrobial compounds suitable for use in this inventionare N-trichloromethylmercapto l-cyclohexene-1,2-dicarboximide andN-(1,1,2,2-tetrachloroethylsulfenyl-cis-A-4-cyclohexene-1,2-dicarboximide.

Preferred antibacterial agents employed herein are salts of2-pyridinethiol-1-oxide which has the following structural formula intautomeric form, the sulfur being attached to the number 2 position ofthe pyridine ring:

| OH N N SH Us 2-pyridinethioll-hydroxyl-oxide 2-pyridinethione Heavymetal salts of the above compounds are sparingly soluble and have a highdegree of antibacterial activity. Preferred salts include zinc, cadmium,tin and zirconium 2-pyridinethiol-1-oxide.

Combinations of the above-described antibacterial substances can also beused to advantage. Such combinations are illustrated in U.S. Pat.3,281,366, granted Oct. 25, 1966.

These antimicrobial compounds are used in particulate form, with averageparticle sizes ranging from about 0.2 to about 30 microns. The quantityof antimicrobial agent employed can range from about 0.1% to about 10%and preferably from about 0.5% to about 2.0% by weight.

Preferred antimicrobial detergent compositions in accordance with thisinvention especially adapted to washing hair and scalp are comprised offrom about to about 35% by weight of at least one non-soap anionic,polar nonionic, ampholytic or zwitterionic surfactant; from about 0.25%to about 2.0% by weight of a watersoluble cationic nitrogen-containingpolymer having a cationic charge density greater than about .001 andhaving an average molecular weight within the range from about 30,000 toabout 1,000,000; from about 0.5% to about 2.0% by weight of awater-soluble or sparingly soluble antimicrobial substance inparticulate form; and the balance substantially water.

Detergent compositions in accordance with this invention can be preparedby methods well known in the art; however, as hereinbefore indicated, ithas been found that especially good results are obtained when thecationic polymer and particulate substances are uniformly admixed in aninitial step, with the mixture then being added to an aqueous solutionor slurry of the surfactant. If the polymeric component and particulatesubstance are added to the surfactant separately, the degree ofdeposition and retention enhancement effected by the polymer will besomewhat less.

Each of the aforementioned components can be incorporated in an aqueousvehicle which may, in addition, include such materials as organicsolvents, such as ethanol; thickeners, such as carboxymethylcellulose,magnesiumaluminum silicate, hydroxyethylcellulose or methylcellulose;perfumes; sequestering agents, such as tetrasodiumethylenediaminetetraacetate; and opacifiers, such as zinc stearate ormagnesium stearate, which are useful in enhancing the appearance orcosmetic properties of the product.

Coconut acyl monoor diethanol amides as suds boosters, and stronglyionizing salts such as sodium chloride and sodium sulfate may be used toadvantage.

Toilet detergent or soap bars containing a cationic polymer andparticulate substance according to this invention can be based on soapor non-soap synthetic detergents and can also contain a variety ofadjuvants to improve product performance or appearance. Examples of suchadjuvants include free fatty acids or cold cream to improve cosmeticproperties, perfumes, inorganic salts to improve bar firmness, insolublesoap to improve bar texture, coloring matter and the like.

In the case of heavy-duty laundering detergents containing the cationicpolymers and particulate substances in accordance with this invention,such detergents can be in granular, flake, liquid or tablet form and cancontain, in addition to detergent and inorganic or organic buildercompounds (such as those disclosed by Diehl in U.S. Pat. 3,159,581,granted Dec. 1, 1964), minor amounts of adjuvant materials which makethe product more effective or more attractive. The following arementioned by way of example. A tarnish inhibitor such as benzotriazoleor ethylenethiourea may also be added in amounts up to about 2%.Fluorescers, perfume and color while not essential in the compositionsof the invention, can be added in amounts up to about 1%. An alkalinematerial or alkali, such as sodium hydroxide or potassium hydroxide, canbe added in minor amounts as supplementary pH adjusters when needed.There can also be mentioned as suitable additives, brightening agents,sodium sulfate, and sodium carbonate.

Corrosion inhibitors generally are also added. Soluble silicates arehighly effective inhibitors and can be added to certain formulas of thisinvention at levels of from about 3% to about 8%. Alkali metal,preferably potassium or sodium, silicates having a weight ratio of SiO:M O of from 1.0:1 to 2.811 can advantageously be used. M in this ratiorefers to sodium or potassium. A sodium silicate having a ratio of SiO:Na O of about 1.6:1 to 2.45:1 is especially preferred for economy andeffectiveness.

In the embodiment of this invention which provides for a built liquiddetergent, a hydrotropic agent at times is found desirable. Suitablehydrotropes are water-soluble alkali metal salts of toluenesulfonate,benzenesulfonate, and xylenesulfonate. The preferred hydrotropes are thepotassium or sodium toluenesulfonates. The hydrotrope salt can be added,if desired, at levels of 1% to about 12%. While a hydrotrope will notordinarily be found necessary, it can be added if so desired, for anyreason including the preparation of a product which retains itshomogeneity at a low temperature.

The term coconut alkyl as used herein and in the following examplesrefers to alkyl groups which are derived from the middle cut of coconutalcohol having the following approximate chain length distribution: 2% C66% C12, 23% C and 9% C Other compounds designated as coconut oilderived are based on unfractionated' coconut oil or its fatty acids.

The following examples are illustrative of several de-' tergentcompositions of this invention.

EXAMPLE I A shampoo composition was prepared having the followingcomposition:

Parts by weight Sodium coconut alkyl glyceryl ether sulfonate (about 23%diglyceryl and the balance substantially monoglyceryl) Sodium tallowalkyl glyceryl ether sulfonate (about 23% diglyceryl and the balancesubstantially monoglyceryl; the tallow alkyls correspond to those ofsubstantially saturated tallow alcohols and contain approximately 2% C32% C and Water Balance 1 Average particle size 2 microns.

Molecular weight 40,000-60,000.

The zinc pyridinethione and ethoxylated polyethylenimine were uniformlyadmixed and added to and uniformly mixed with the balance of thecomponents. The resulting product was a stable cream having excellentcosmetic and antidandrutf properties. The degree of deposition of zincpyridinethione from this composition was.

much greater than the degree of deposition attained with a similarlyformulated product which contained no cationic polymer. Residualantimicrobial activity of surfaces washed with this composition ismarkedly greater as compared to surfaces washed with a control productwithout polymer.

Compositions identical to the composition of Example I, but containing 5micron diameter particles of 3,4,4- trichlorocarbanilide; 3,4',5tribromosalicylanilide; 4,4- dichloro 3 (trifluoromethyl)carbanilide;and bis(2- hydroxy 3,5,6 trichlorophenyDmethane, and 6.5 mi- 11 mer isfound to be substantially greater than is attached with the controlcompositions, and a corresponding increase in residual antimicrobialactivity is observed on surfaces washed therewith.

EXAMPLE II Another antimicrobial detergent formulation in accordancewith this invention is formulated as follows:

Parts by weight Triethanolamine coconut alkyl sulfate 10.0

Coconut alkyl dimethyl amine oxide 10.0 Monoethanol amide of coconutfatty acids 5.0 Ethanol 10.0 Polyethylenimine 1 0.75 Cadmium2-pyridinethiol-l-oxide (average particle size 3.0 microns) 0.25 Water,NaOH to adjust to pH 8.5 balance 1 A water-soluble cationic polymerhaving a molecular weight of 50,000 to 100,000, a cationic chargedensity of .004 in aqueous solution alt pH 7.0, and la viscosity of 2.5centipqise (absolute viscosity) in. 'a 1% by weight aqueous solutionmeasured with an Ostwaild viscosimeter at 100 F.

Triethanolamine coconut alkyl sulfate 20.0 Monoethanol amide of coconutfatty acid 4.5 Magnesium aluminum silicate 0.9 Methylcellulose 0.23 Dye0.008 Perfume 08 Zinc 2-pyridinethiol-1-oxide 1 1.0 Polyethylenimine/ethylene oxide reaction prodduct (weight ratio 4:1; molecular weight50,000;

cationic charge density .004 in aqueous solution at pH 7.0) 0.5 Waterbalance 1 Average particle size 1.5 microns. 2 Molecular weight 10,000.

This composition provides a substantial degree of antidandruff elfectwhen used in the customary fashion. The degree of deposition andretention of particulate zinc pyridinethione on the hair and scalp aftershampooing with this product is substantially greater than is attainedwith a similar composition without the polyethylenimine/ ethylene oxidereaction product.

Sodium coconut alkyl (ethoxy) sulfate Sodium lauroyl sarcosinate Sodiumdodecyl benzene sullonate. 2-trimethylamine laurie acid 'Iriethanolaminecoconut alkyl mono lye ride sulfonate Potassium coconut soap.-. EthanolPolyethylenimine 1 Polyethyleniminel /propylene oxide reaction product 2.1. i6

Tin Z-pyridmethiol-l-oxide (average particle size 7 microns) Zirconium2-pyridinethiol-1-oxide (average particle size 4 microns) Water nutalkyl dimethyl ammonium chloride can be used in place of sodium dodecylbenzene sulfonate without loss of the improved deposition and retentionof zirconium 2-pyridinethiol-l-oxide particles effected by thepolyethylemmine.

In Example IV, sodium coconut alkyl (ethoxy) sulfate can be replacedwith the condensation product of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide 'with propylene glycol and:having a molecular weight of 1600 or the condensat1on product of octylphenol and ethylene oxide using a 1mole ratio of 1:15, withsubstantially equivalent resu ts.

The enhanced deposition and retention of pyridinethione salts wasdemonstrated as follows: A control composition was formulated as inExample I, but omitting the polyethylenimine/ethylene oxide reactionproduct. A composition similar in formulation but containing 0.5% ofpolyethylenimine having a cationic charge density of .004 in aqueoussolution at pH 7.0 and a molecular weight Of 50,000 was prepared anddesignated test composition A. A test composition designated B whichdiffered from the control composition in containing 0.5% of thepolyethylenimine of composition A and 1.0% of zincZ-pyridine-thiol-l-oxide having an average particle size of 2 micronsrather than 2.0% of this latter component as in the control composition,was also prepared.

The hair of 16 female subjects was shampooed by experienced beauty shopoperators who washed half of the hair and scalp of each subject with thecontrol composition. The other half of the subjects hair and scalp waswashed in the assigned test composition. The test and controlcomposition were used ad libitum, in quantities sufficient to provide agood lather. After lathering for 45 seconds, the hair was rinsed and thecompositions were reapplied, lathered for 45 seconds and rinsed again.The hair was then dried. A sample of cornified epithelium from both thecontrol and test halves of each subjects scalp was obtained by applyingcellulose adhesive tape against the scalp. The tape was then placed on aglass slide with the adhesive in contact with the glass. The slide wasexamined with a polarizing microscope at approximately 400 diameterswith polaroids crossed. While the cornified epithelium exhibited somedegree of birefringence, the highly anisotropic properties of theparticulate zinc 2-pyridinethiol-l-oxide made it readily visible undersuch 'viewing conditions. The relative quantity of particulate zincZ-pryidinethiol 1 oxide was then graded on a 0 to 4 scale, with a gradeof 4 indicating heavy deposition, and 0 indicating substantially nodeposition.

Examples V11 VIII 1 Molecular weight 10,000; cationic charge density.004 in aqueous solu 2 Weight ratio 2:1; molecular weight 30,000;cationic charge density gre tion at pH 7.0. ater than .001 in aqueoussolution at pH 7.0.

The following results were obtained.

It can be seen from the above results that deposition and retention ofzinc Z-pyridinethiol-l-oxide was substantially greater from a detergentcomposition which contained 0.5 of polyethylenimine as compared to thecontrol composition which contained the same amount of zinc2-pyridinethiol-l-oxide without polymer. Similarly, composition B whichcontained only 1.0% of Zinc 2-pyridinethiol-l-oxide yielded a somewhathigher degree of deposition and retention than the control compositionwhich contained twice as much of this salt, but no polymer.

In like manner the relative deposition of zinc 2-pyridinethiol-l-oxidefrom a detergent composition containing various concentrations ofethoxylated polyethylenimine was demonstrated as follows: The followingcompositions were prepared.

TABLE 2 Parts by weight Composition Control C D E Sodium coconut alkylglyceryl ether sulionate 1 Sodium tallow alkyl glyceryl ethe sultonateSodium chloride Sodium sulfate Sodium N-lauroylsarcosinate N-coconutacyl sarcosinate Coconut acyl diethanolannde Acetylated lanolin PerfumeZine 2-pyridinethio ide (average particle size 2 microns)Polyethylenimine/ethylene oxide reaction product I Water was Balance 1Same as Example 1.

Each of the compositions was tested in the manner described supra, usinga test composition and control composition on each of the test subjects.The results attained were as follows:

Average degree of deposition It can be seen that the degree ofdeposition attained with composition C containing only half as much zincZ-pyridinethiol-l-oxide as the control was yet greater than the control.Composition D, which contains 1.0% polymer and only A as much zincZ-pyridinethiol-l-oxide than the control displayed only moderately lessdeposition than the control. Composition E, which contains 2% polymerand only half as much zinc 2-pyridinethiol-loxide as the control,provides somewhat greater deposition than the control. Composition F,containing 2.0% polymer and only A as much zinc 2-pyridinethiol-l-oxideas the control, provides a degree of deposition approximately equal tothe control.

The degree of enhancement of particle deposition and retention in thepresence of cationic polymer is also demonstrated by the Slide ParticleDeposition test conducted as follows:

Dandruff scales are collected from the scalps of afflicted individualsand mounted on glass slides with a clear acrylic adhesive. The dandruffslides are covered with a clean white polyester/cotton cloth, wettedwith water, and washed with a test detergent composition by brushing thecloth-covered slide with a soft toothbrush and using 20 grams of thedetergent composition for 50 strokes. The slides are then rinsed for oneminute with cloth in place and then for two minutes with cloth re- 14moved. The rinse water used is tap water at 37 C. with a flow rate of 4liters per minute. The slides are then allowed to dry.

The washed slides are examined microscopically at 400 diametersmagnification using cross polarized filters. Deposition is graded on a0-4 scale, no deposition being given a 0 grade, while maximum expecteddeposition is given a 4 grade. Grades in between vary approximatelylinearly with the density of deposited particles. Several areas of eachslide are given whole number grades before the average for that slide istaken to the nearest of a deposition grade. In each test three slidesfor each test material are treated in random order. All grading andwashing is done on a blind basis.

Detergent compositions substantially corresponding to the composition ofExample I but containing 0.5% by weight of zinc Z-pyridinethiol-l-oxideand 2.0% by 'weight of various cationic polymers of this invention weretested against a control composition without polymer using the methoddescribed above. The following results were obtained.

1 Ethoxylated polyethylenimine as in Example I.

2 Polyvinylimidazole substantially completely quaternized with dimethylsulfate, having a molecular Weight of from 5 to 20 X 10 and a cationiccharge density of .009.

3 Poly(dimethylaminoethylmethaerylate) substantially completelyquaternized with methyl phosphate, having a molecular weight between1,000 and 5,000,000 and a cationic charge density of .006.

Poly(diethylaminoethylmethacrylate) substantially quaternized withdimethyl sulfate, having a molecular weight within tlfle tinge fromabout 1,000 and 5,000,000 and a cationic charge density 0 .00

completely -It can be seen that substantial enhancement of particledeposition and retention is effected by the inclusion of representativecationic polymers in detergent formulations containing same.

EXAMPLE XII An antimicrobial milled toilet detergent bar which alsoconstitutes a preferred embodiment of this invention is prepared inaccordance with methods well known in the art and having the followingcomposition:

Parts by weight Sodium alkyl glyceryl ether sulfonate 1 8.0 Potassiumalkyl sulfate 1 20.0 Magnesium soap of :20 tallow: coconut fatty acids16.7 Sodium soap of 80:20 tallow: coconut fatty acids 32.4 Inorganicsalts (sodium and potassium chlorides and sulfates) 9.23,4,S-tribromosalicylanilide (Average particle size 5 microns) 1.0Cationic polymer 2 2 0 Water and miscellaneous 10:7

1 Alkyl groups derived from middle cut of alcohols obtained by catalyticreduction of coconut alcohol which has a chain length distributionsubstantially as follows: 2% C10, 66 C12, 23% C14, and 9% C16.

Quaternary ammonium-substituted hydroxyethylcellulose ether formed byreacting a hydroxyethylcellulose ether (havi-ng a degree of substitutionwith hydroxyethyl groups of 1.3) with the reaction product of 0.7 moleepiclmlorohydrin and 0.7 mole of Itrimethylamine per substitutedanhydroglucose unit thereof, said polymer having a cationic chargedensity of .002 and a molecular weight within the range from about200,000 %to 230,000.

The deposition and retention of the particulate antimicrobial agent3,4',S-tribromosalicylanilide upon skin washed with the abovecomposition is substantially greater 15 than H occurs with 7 a controlcomposition without cationic polymer.

Toilet detergent bars identical in composition to the bar describedabove are prepared, replacing the 3,4,5-tribromosalicylanilide with 4micron particles of the antimicrobial agents3,4,4'-trichlorocarbanilide; 4,4'-dichloro-3-(trifluoromethyl)carbanilide; bis(2 hydroxy3,5,6-trichlorophenyl)methane; and a 1:1 mixture of 4,4-dichloro-3-(trifluoromethyl)carbanilide and 3,4,5-tribromosalicylanilide,respectively, with improved deposition and retention of theantimicrobial particles being attained in each case. relative to controlcompositions without cationic polymer.

Additional toilet detergent bars are prepared as in Example XII eachcontaining one of the following cationic polymers in place of thequaternary ammonium-substituted cellulose ether polymer employedtherein:

(1) Nalcolyte 605, as hereinbefore defined.

(2) Coagulant Aid 225, as hereinbefore defined.

(3) Conductive Polymer 261, as hereinbefore defined.

(4) Poly-vinylimidazole substantially completely quarternized withdimethyl sulfate, having a molecular weight of 5,000, and a cationiccharge density of .009.

(5) Poly(dimethylaminoethylmethacrylate) substantially completelyquarternized with methyl phosphate, having a molecular weight of1,000,000, and a cationic charge density of .006.

(6) Poly(diethylaminoeth'ylmethacrylate) substantially completelyquaternized with dimethyl sulfate, having a molecular weight of 300,000,and a cationic charge density of .005.

Each of these toilet detergent bars provides a degree of3,4,5-tribromosalicylanilide particle deposition and retention on skinwashed therewith which is substantially greater than is attained withtoilet detergent control bars without such polymers.

IEXAMPLE XIII An antimicrobial granular built laundry detergent prodnetis prepared by conventional means, having the following composition:

:Parts by weight Sodium alkyl benzene sulfonate (the alkyl groupaveraging about 12 carbon atoms and being derived from polypropylene)17.5 Sodium tripolyphosphate 49.7 Sodium sulfate 13.3

Silicate solids 7. 0 3,4,4'-trichlorocarbanilide (particle sizeaveraging 3 microns) 0.5 Quaternized polyvinylimidazole 1.5

Polyvinylimirlazole in which 80% of the vinylirnidazole units arequarternized with dimethyl sulfate, having a molecular weight of 250,000and a cationic charge density of .007.

Fabris laundered in this product retain a substantially greater quantityof 3,4,4'-trichlorocarbanilide particles than do fabrics washed in acontrol product formulated as above, but 'without the cationic polymer.

Each of the foregoing examples describe embodiments of this inventionwhich involve antimicrobial particulate substances. Ashereinbeforedisclosed, the deposition and retention of other particulate substancesare also enhanced by the cationic polymers. The following examples areillustrative of detergent compositions in accordance withthis inventioncontaining representative particulate substances which function throughdeposition and retention, on washed surfaces.

Toilet detergent bars desirably contain a sunscreen or ultravioletabsorber which will deposit on the skin in the course of washingtherewith to provide protection against harmful sun rays. Suitableparticulate ultraviolet absorberswhich can be incorporated in detergentbars for this purpose include, for example,2-hydroxy-4-n-octoxybenzophenone, 2 hydroxy4-methoxy-2-carboxybenzophenone, and .2rhydI'QXY:4:methQXbQI ZQPhQnQnQ-.=Thfisfi materials are insoluble particulate solids which are employedin bar soap formulations in concentrations ranging from about 1% toabout 5% by weight.

EXAMPLE XIY A toilet soap bar containing ,an ultraviolet absorber isformulated in accordance with this invention as follows: Percent byweight Sodium soap of 50:50 itallow-zcoconut fatty acids 13.19 Coconutfatty acid 7.30 Cold cream 1.10

Inorganic salts (sodium chloride and sulfate and 1 Same as Example XII.

When used in the customary fashion, the toilet soap bar of this exampleeffects a substantially greater degree of deposition and retention ofthe particulate ultraviolet asborber (2-hydroxy-4-n-octoxybenzophenone)on the washed skin surfaces than does an identical composition withoutpolymer.

Additional toilet so'ap bars are prepared as above but containingZ-hydroxy-4 methoxy-2'-carboxybenzophenone and2-hydroxy-4-methoxybenzophenone, respectively, in place of2-hydroxy-4-n-octoxybenzophenone, with substantially equivalent results'v 1 Toilet soap bars formulated in accordance with Example XIV areprepared containing polyvinylimidazole substantially completelyquaternized with dimethyl sul-' fate, having a molecular weight of200,000 and a cationic charge density of .009; quaternizedpoly(p-dirnethylaminomethylstyrene) having a molecular weight of 250,000and a cationiccharge density of .006; and JR-1L, a quaternaryammonium-substituted cellulose derivative supplied by Union Carbide,having a molecular weight within the range from 100,000 to 1,000,000,and a cationic charge density of .004; respectively, in place of thecationic polymer employed in that example. The resulting products aresubstantially equivalent to the product of Example XIV in terms ofparticle deposition and retention.

Other insoluble particulatesubstances which are desirably incorporatedin toilet soap or detergent bars include the so-called skin feelenhancers. Such materials are deposited as particles on the skin in thecourse of washing and create a favorable skin feel after washing. Suchmaterials include, for example, nicotinic acid, talc and silicones, suchas Dow-Corning Silicone F-157. These materials are desirablyincorporatedin a toiletbar formula at levels of about 10% by weight.

EXAMPLE XV A bar soap formulation as set forth in Example XIV isprepared substituting 10.2% by weight of nicotinic acid particles(average particlesize 5 microns) for the2-hydroxy-4-n-octoxybenzophenone and "coconut fatty acid. The resultingcomposition yields a substantially greater degree of deposition andretention of nicotinic acid particles on skin washed with the bar thanis attained with a bar similarly formulated but without cationicpolymer. Similar results are obtained when Dow-Co rn' 17' used inheavy-duty laundry detergent products in concentrations up to about 1%by weight.

EXAMPLE XVI A built liquid detergent formulation containing aparticulate bluing material and a cationic polymer in accordance withthis invention is formulated as follows:

Percent by weight 3 (N,Ndimethyl-N-coconutammonio)-2-hydroxypropane-l-sulfonate 9.00 Tergitol12-P-12 (condensation product of 12 moles of ethylene oxide and one moleof dodecyl- 1 phenol) 3.00

Tripotassium methylene diphosphonate 26.00

Sodium silicate (SiO :Na O=1.6:1) 3.00 Potassium toluenesulfonate 8.50Sodium carboxymethylhydroxyethylcellulose 0.30 Ultramarine blue(particle size 1.8 microns) 0.15 Cationic polymer 3.5 Water BalanceParts by weight XVII XVIII Example Sodium coconut alkyl glyceryl ethersullonate 1 Sodium talloW alkyl glyceryl ether sulionate Sodium suliateSodium N-lauroylsarcosinate- N-coconut aeyl sarcosine Diethanolamide ofcoconut fatty acids-.. Acetylated lanolin Zinc 2-pyridinethiol-1-oxideN-Trichloromethylruerca t-4-cyc hexene-1,2-dicarboximi e 4 0.5N-(1,1,2,2-tetraehloroethylsulfenyl)-cisA-4-eyelohexene-1,2-dicarboximido 5 1. 0 Polymer (1) XIX XX 1 About 23%diglyceryl and the balance substantially moneglyceryl.

2 About 23% diglyceryl and the balance substantially monoglyceryl; thetallow alkyls correspond to those of substantially saturated tallowalcohols and contain approximately 2% Cu, 32% C and 66% 0 s.

8 Average particle size 2 microns.

4 Average particle size 6.5 microns.

5 Average particle size 10.0 microns.

No'rns:

Polymer (1) in the above example is poly (diethlaminoethylmethacrylate)substantially completely quaternized with dimethylsuliate, hfazig amolecular weight of 2,000,000 and a cationic charge density 0 Polymer(2) is JR-IL.

Polymer (3) is polyethylenimine/ethylene oxide reaction product (weightratio 1:1) molecular weight 80,000120,000 and cationic charge density of.004 in aqueous solution at pH 7.0.

Polymer (4) is primafloe C-3.

Each of the above compositions provides a substantially greater degreeof deposition and retention of the particulate antimicrobial agentscontained therein than similar compositions formulated without thesepolymers.

It will be obvious to those skilled in the art that the concept of thisinvention is applicable to a wide variety of insoluble or sparinglysoluble particulate substances in addition to those specificallydescribed in the foregoing specification. For example, perfumes whichhave been adsorbed on insoluble particulate resinous substances can bedeposited on skin, fabrics and other surfaces washed with detergentcompositions containing same to a substantially greater degree, throughthe inclusion in said compositions of a cationic polymer as hereindefined.

1.A detergent composition consisting essentially of: (I) from about 2%to about of an organic surfactant selected from the group consisting ofanionic, ampholytic, polar nonionic, nonionic, and zwitterionicsurfactants and cationic surfactants selected What is claimed is:

from the group consisting of distearyldimethyb. chloridestearyldimethylbenzylammoammonium nium chloride,coconutalkyldimethylbenzylammonium chloride,dicoconutalkyldimethylammonium chloride, cetylpyridinium chloride, andcetyltrimethylammonium bromide;

(II) from about 0.25% to about 4% of quaternary ammonium substitutedcellulose derivatives having molecular weights within the range fromabout 2,000 to about 3,000,000 and cationic charge densities greaterthan .001 said derivatives containing as substituents groups selectedfrom the group consisting of lower alkyls, lower hydroxy alkyls,polyethoxy groups containing up to twenty ethoxy units, and quaternaryammonium groups having the general formula:

wherein m is an integer from 0 to 10, n is an integer from 1 to 3, and pis an integer from 0 to 10;

(III) from about 0.1% to about 10% of a waterinsoluble or sparinglysoluble particulate substance having an average diameter within therange from 0.2 to 30 microns, selected from the group consisting of:

(A) antimicrobial substances selected from the group consisting of:

(1) substituted salicylanilides having the general formula:

Y OH E) Y Y X Y wherein X is hydrogen or halogen, and Y is hydrogen,halogen or trifluoromethyl;

(2) substituted carbanilides having the general structural formula:

Y (I? Y wherein Y is hydrogen, halogen, or trifluoromethyl, X is halogenor ethoxy, X is hydrogen or halogen;

(3) substituted bisphenols having the general structural formula:

wherein X is a halogen and n is an integer from 1 to 3, R is an alkyleneradical having from 1 to 4 carbon atoms or divalent sulfur;

(4) N trichloromethylmercapto-4-cyclohexene-1,2-dicarboximide;

(5) N (1,1,2,2-tetrachloroethylsulfenyl)-cis-A-4-cyclohexene-1,2-dicarboximide;

(6) heavy metal salts of 2-pyridinethiol-loxide selected from the groupconsisting of zinc, cadmium, tin, and zirconium salts; and

(7) combination thereof;

19 (B) ultraviolet absorbers selected from the group consisting of2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy 2'carboxybenzophenone, and 2-hydroxy-4-methoxybenzophenone; and (C)ultramarine blue. 2. The composition of claim 1 wherein the cationicpolymer is a quaternary ammonium substituted cellulose ether derivativehaving the formula:

wherein R0911 is the residue of an anhydroglucose unit, Y is an integerfrom 50 to 20,000, and each R has the general formula:

wherein m is an integer from to 10, n is an integer from 0 to 3, and pis an integer from 0 to 10.

3. The composition of claim 1 wherein the cationic polymer is aquaternary ammonium-substituted cellulose ether derivative formed byreacting a hydroxyethylcellulose ether having a degree of substitutionwith hydroxyethyl groups of 1.3 with the reaction product of 0.7 mole ofepichlorohydrin and 0.7 mole of trimethylamine per substitutedanhydroglucose unit thereof.

- 4. The composition of claim 1 wherein the particulate substance is anantimicrobial substance.

5. The composition of claim 4 wherein the particulate substance is aheavy metal salt of 2-pyridinethiol-1-oxide wherein said heavy metalsalt is selected fromthe group consisting of zinc, cadmium, tin, andzirconium salts.

6. The composition of claim 5 wherein the heavy metal salt is zinc.

7. The composition of claim 2 wherein the particulate substance is anantimicrobial substance.

8. The composition of claim 7 wherein the particulate substance is aheavy metal salt of Z-pyridinethiol-l-oxide wherein said heavy metal isselected from the group consisting of zinc, cadmium, tin, and zirconiumsalts.

9. The composition of claim 8 wherein the heavy metal 1s zinc;

10. The composition of claim 1 wherein the detergent is a water-solublesalt of a member selected from the group consisting of higher fattyacids, anionic organic sulfuric reaction products having in theirmolecular structure an alkyl group containing from about 8 to about 20carbon atoms and a sulfuric or sulfonic acid ester radical, and acylsarcosinates, wherein the acyl group contains from about 10 to about 18carbon atoms.

References Cited UNITED STATES PATENTS 2,768,162 10/1956 Evans 260-232X2,891,025 6/1959 Price 252-152X 3,080,264 3/1963 Zimrnie et al. 134223,235,455 2/1966 Judge et al. 252l07X 3,236,733 2/1966 Karsten et al252107X 3,313,734 4/1967 Lang et a1 252-152 3,400,148 9/1968 Quimby252-137X LEON D. ROSDOL, Primary Examiner M. HALPERN, Assistant ExaminerUS. Cl. X.R.

POW? UNITED STATES PATENT OFFICE 5 CERTIFICATE OF CORRECTION Patent No.3,580,853 Dated May 25, 197 1 Inventor(s) John J. Parran, Jr

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 3 line 47, the second "amine" should be deleted. -1 Column 4,lines 23 and 24, the second phrase "or alkyl aromatic" should bedeleted.

Column 4, line 24, "are" should read -art-.

Column 5, line 38, "Esslemann" should read -Esselmann-.

Column 6, line 5, "anhydroglycose" should read --anhydroglucose---.Column 6, line 32, "particuarly" should read -particularly-. Column 6,line 37, "JA-lL" should read --JRlL-- Column 6, line 65, "-HC-C (R C"should read --HCC (R')-C--. Column 8, line 5, "HHCNH" should read---N'HCNH-.

Column 12, line 26, "2-pyridine-thiol-l-oxide" should read-2pyridinethiol-loxide-.

Column 13, line 27, "Sodium N-lauroylsarcosinate" should read -SodiumN-lauroyl sarcosinate--.

Column 13, line 55, "than" should read -as.

Column 13, line 55, after "control" should read Column 15, line 22,"quarter-" should read quater---. Column 15, line 26, "quarternized"should read ---quaternized-. Column 15, line 56, "Fabris" should read-Fabrics--. Column 16, line 28, "asborber should read -absorber--.Column 17, line 40, "Sodium N-lauroylsarcosinate" should read SodiumN-lauroyl sarcosinate-.

Cgugn 17, line 52 "2% C 32% C should read --2% C Signed and sealed thislet day of May 1973 (bnAL) Attest:

.J EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting OfficerCommissioner of Patents

